EP0220603B1 - Procédé de préparation de polymères en forme de poudre - Google Patents

Procédé de préparation de polymères en forme de poudre Download PDF

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Publication number
EP0220603B1
EP0220603B1 EP86114235A EP86114235A EP0220603B1 EP 0220603 B1 EP0220603 B1 EP 0220603B1 EP 86114235 A EP86114235 A EP 86114235A EP 86114235 A EP86114235 A EP 86114235A EP 0220603 B1 EP0220603 B1 EP 0220603B1
Authority
EP
European Patent Office
Prior art keywords
carbon dioxide
weight
vinyl
polymerization
vinylformamide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP86114235A
Other languages
German (de)
English (en)
Other versions
EP0220603A1 (fr
Inventor
Heinrich Dr. Hartmann
Walter Denzinger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
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BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE19853537455 external-priority patent/DE3537455A1/de
Priority claimed from DE19853537457 external-priority patent/DE3537457A1/de
Application filed by BASF SE filed Critical BASF SE
Priority to AT86114235T priority Critical patent/ATE46351T1/de
Publication of EP0220603A1 publication Critical patent/EP0220603A1/fr
Application granted granted Critical
Publication of EP0220603B1 publication Critical patent/EP0220603B1/fr
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/04—Polymerisation in solution
    • C08F2/06—Organic solvent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F26/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • Powdery polymers can be prepared by polymerizing monomers by various methods, e.g. by the method of precipitation polymerization, reverse suspension polymerization or in a powder bed. In all cases you need a diluent. In the production of water-soluble, powdery homopolymers, aliphatic or aromatic hydrocarbons are used, for example, as diluents. When polymerizing in a fixed bed, inert liquids are required as boiling aids or a large excess of a volatile monomer is used to remove the heat generated during the polymerization. The inert liquids used in the polymerization must be removed or recovered from the polymers. The removal of small amounts of aromatic hydrocarbons or halogenated hydrocarbons from water-soluble polymers is particularly problematic.
  • carboxylic acids can be obtained from dilute aqueous solutions of alkali metal salts of carboxylic acids in that the aqueous solutions of alkali metal salts of carboxylic acids at temperatures from 35 to 200 ° C and pressures from 80 to 500 atm treated with a supercritical fluid containing at least 10 mole% carbon dioxide. Under the reaction conditions, the salt of the carboxylic acid forms the free carboxylic acid, which dissolves in the supercritical liquid and is isolated therefrom by reducing the pressure.
  • a process for the preparation of polymers is known from US Pat. No. 3,522,228, in which ethylenically unsaturated monomers are present in the presence of catalysts or by the action of high-energy radiation in liquid carbon dioxide at temperatures from -78 to 100 ° C. under increased pressure of the homo- or subject to copolymerization.
  • the polymers are obtained in the form of coarser powders or viscous oils, from which they are precipitated by treatment with liquids in which the polymers do not dissolve.
  • the object of the present invention is to provide a process according to which particularly finely divided powdery polymers are obtained by polymerizing the monomers in a diluent which is physiologically harmless and can be easily removed from the polymers.
  • the object is achieved according to the invention with a process for the preparation of pulverulent polymers by polymerizing ethylenically unsaturated compounds in carbon dioxide under pressure in the presence of free radical initiators and evaporating the carbon dioxide if, as ethylenically unsaturated compounds, N-vinylcarboxamides, water-soluble esters of ethylenically unsaturated carboxylic acids , N-vinyl lactams, N-vinyl imidazoles, N-vinyl imidazolines homopolymerized and N-vinyl formamide copolymerized with N-vinyl pyrrolidone or vinyl acetate, the polymerization in supercritical carbon dioxide with mixing at temperatures of about 31 to 150 ° C and pressures above 73 bar is carried out and 100 to 1500 parts by weight of carbon dioxide are used per 100 parts by weight of monomer.
  • N-vinyl carboxamides suitable for the preparation of homopolymers are, for example, those monomers which are derived from N-vinyl carboxamides from saturated G to Cs carboxylic acids, e.g. N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methyl-acetamide, N-vinylpropionamide, N-vinyl-N-methylpropionamide, N-vinylbutyramide and N-vinylcapronamide as well Suitable N-vinyl lactams are, for example, N-vinyl pyrrolidone and N-vinyl caprolactam.
  • water-soluble esters of monoethylenically unsaturated carboxylic acids Preferable to use the water-soluble esters of ethylenically unsaturated Cs- to C s -carboxylic acids.
  • the water-soluble esters of ethylenically unsaturated carboxylic acids are derived either from amino alcohols or from glycols or polyglycols, only one OH group of the glycols and polyglycols being esterified with one ethylenically unsaturated carboxylic acid.
  • Suitable esters of this type are, for example, DI-C1- to C 3 -alkylamino-C 2 - to Cs-alkyl- (meth) -acrylates, such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dipropylaminoethyl acrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, dimethylaminopethylamine, dimethylaminophenyl amine, dimethylaminopethylamine and dimethylaminohexyl acrylate.
  • DI-C1- to C 3 -alkylamino-C 2 - to Cs-alkyl- (meth) -acrylates such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethy
  • the basic acrylates are used in the form of the free bases, the salts with mineral acids, for example hydrochloric acid or sulfuric acid, or in quaternized form (suitable quaternizing agents are, for example, dimethyl sulfate, methyl chloride, ethyl chloride or benzyl chloride).
  • Suitable esters of glycols, polyglycols or polyhydric alcohols, each of which only one hydroxyl group is esterified are, for example, hydroxyethyl acrylate, hydroxyethyl methacrylate and acrylic acid monoesters of polyalkylene glycols having a molecular weight of 1500 to 10,000 in a molar ratio of 1: 1, the corresponding methacrylic acid esters and esters of acrylic acid and methacrylic acid with block copolymers of ethylene oxide and propylene oxide, in which the molar ratio of ethylenically unsaturated carboxylic acid to alcohol is 1: 1.
  • the salts or quaternization products of the basic esters and the hydroxyalkyl esters of the ethylenically unsaturated carboxylic acids form homopolymers which dissolve in water.
  • the homopolymers of N-vinylpyrrolidone and N-vinylcaprolactam are also water-soluble.
  • N-vinylimidazole and substituted N-vinylimidazoles are also suitable as monomers for the process according to the invention for the preparation of homopolymers.
  • N-vinylimidazole and substituted N-vinylimidazoles for example.
  • N-vinylimidazoles and N-vinylimidazolines are used in neutralized or in quaternized form with mineral acids, the quaternization preferably being carried out with dimethyl sulfate, benzyl chloride, methyl chloride or ethyl chloride.
  • the homopolymers are preferably prepared from N-vinylformamide, N-vinyl-N-methylformamide, N-vinylpyrrolidone, hydroxyethyl acrylate, hydroxyethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate and diethylaminoethyl acrylate.
  • the basic monomers can also be used in the form of the salt with strong mineral acids or in quaternized form.
  • Copolymers of N-vinylformamide and N-vinylpyrrolidone and copolymers of N-vinylformamide and vinyl acetate are of technical interest.
  • N-vinylformamide and N-vinylpyrrolidone can be copolymerized in any ratio.
  • the copolymers of N-vinylformamide and vinyl acetate are prepared by copolymerizing monomer mixtures which contain up to 90% by weight, preferably 5 to 60% by weight, of vinyl acetate. All monomers are preferably used in the polymerization in anhydrous form.
  • the polymerization is carried out under pressure in supercritical carbon dioxide as an inert diluent.
  • JA Hvatt J. Org. Chem. 49, 5097-5101 (1984) reports on the properties of carbon dioxide in the liquid and in the supercritical state.
  • the critical point for carbon dioxide is then around 31 ° C and 73 bar.
  • the homo- and copolymerization of the above-mentioned monomers takes place in supercritical carbon dioxide at temperatures above about 31 ° C., the critical temperature of the carbon dioxide.
  • the upper limit for the preparation of the polymers is that temperature which is 10 ° C. below the beginning of the softening range of the resulting polymers.
  • the upper value for this temperature limit is 150 ° C.
  • the homo- and copolymerization is preferably carried out in the temperature range from 40 to 130 ° C., in particular 70 to 130 ° C.
  • the pressures are above 73 bar, preferably in the range from 80 to 300 bar.
  • redox coinitiators for example benzoin, dimethylaniline and organically soluble complexes and salts of heavy metals such as copper, cobalt, manganese, iron, nickel and chromium
  • the half-lives of the peroxides mentioned, especially the hydroperoxides can be reduced, so that for example tert-butyl hydroperoxide in the presence of 5 ppm copper (II) acetylacetonate is already effective at 100 ° C.
  • the polymerization initiators are used in the amounts customary in polymerizations, e.g. 0.05 to 10, preferably 0.1 to 5 parts by weight of an initiator are required per 100 parts by weight of the monomers.
  • the polymerization can optionally also be carried out in the presence of polymerization regulators in order to regulate the molecular weight of the polymers. If you want to produce particularly low molecular weight copolymers, higher amounts of polymerization regulators are used, while only small amounts of polymerization regulators are used for the production of high molecular weight copolymers or work in the absence of these substances.
  • Suitable polymerization regulators are, for example, 2-mercapto-ethanol, mercaptopropanols, mercaptobutanols, thioglycolic acid, n-dodecyl mercaptan, tert-dodecyl mercaptan, thiophenol, mercaptopropionic acid, allyl alcohol and acetaldehyde.
  • the polymerization regulators are used in an amount of 0.05 to 10, preferably 0.1 to 5% by weight, based on the amount of the monomer used.
  • the polymerization reaction can be carried out batchwise or continuously in appropriately designed printing apparatuses.
  • the printing apparatuses In order to dissipate the heat generated during the polymerization, it is desirable that the printing apparatuses have a cooling system. Of course, they must also be heatable in order to heat the reaction mixture to the temperature desired for the polymerization.
  • the pressure equipment must have mixing devices, e.g. Stirrers (blade, impeller or multi-stage impulse countercurrent stirrers) or blades.
  • the pressure polymerization can be carried out, for example, by first introducing a certain amount of a monomer and the initiator into a pressure apparatus, then introducing carbon dioxide in liquid form and, after closing the autoclave, heating the reaction mixture to the polymerization temperature.
  • Another possibility is to put only a part of the amount of monomer in the total amount of carbon dioxide required in the autoclave and to pump the remaining amount of monomer together with the initiator into the autoclave after the polymerization has progressed. Good mixing of the reaction mass must be ensured during the polymerization.
  • the reaction mixture is cooled, if appropriate, and the carbon dioxide is separated off.
  • the homopolymers and copolymers are obtained as a powdery residue.
  • the particle size of the powder is 0.5 ⁇ m to 0.5 mm, preferably 1 ⁇ m to 0.5 mm, these particles consisting of primary particles of 0.5 to 3 ⁇ m in diameter and more or less loosely aggregated.
  • homopolymers with a Fikentscher K value of 10 to 300, preferably 20 to 200, are obtained.
  • the homopolymers are, apart from a few exceptions, water-soluble, and at least 10 g homopolymers dissolve per liter Water.
  • the homopolymers of N-vinylformamide and N-vinylpyrrolidone are of particular interest.
  • the homopolymers of N-vinylformamide can be converted into polymers by treatment with bases or acids which, in addition to unchanged polymerized N-vinylformamide units, contain N-vinylamine units.
  • Such polymers are highly effective flocculants in sewage sludge dewatering and drainage and retention agents in the manufacture of paper.
  • Homopolymers which can be prepared by the process according to the invention can also be used e.g. as builders in detergents and as sizing agents, raw materials for glue, sizes and / or strengthening agents for paper and in the tertiary production of petroleum.
  • the K values were determined according to H. Fikentscher, Cellulose-Chemie 13, 58 to 64 and 71 to 74 (1932) in 5% saline solution at a polymer concentration of 0.1% by weight and a temperature of 25 ° C.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Claims (4)

1. Procédé de préparation de polymères en poudre par polymérisation de composés éthyléniquement insaturés dans du dioxyde de carbone, sous pression et en présence d'initiateurs formateurs de radicaux, et par vaporisation du dioxyde de carbone, caractérisé en ce que, comme composés éthyléniquement insaturés, on homopolymérise des N-vi- nylamides d'acides carboxyliques, des esters solubles dans l'eau d'acides carboxyliques éthyléniquement insaturés, des N-vinylactames, des N-vinylimidazoles, des N-vinylimidazolines et on copolymérise le N-vinylformamide avec la N-vinylpyrrolidone ou avec jusqu'à 90% en poids d'acétate de vinyle, en effectuant chaque fois la polymérisation dans du dioxyde de carbone au-dessus de ses conditions critiques, par mélange à des températures d'environ 31 à 150°C et sous des pressions supérieures à 73 bars, et en mettant en oevre, pour 100 parties en poids de monomère, 100 à 1500 parties en poids de dioxyde de carbone.
2. Procédé suivant la revendication 1, caractérisé en ce que l'on met en oeuvre, pour 100 parties en poids de monomère, 200 à 900 parties en poids de dioxyde de carbone.
3. Procédé suivant les revendications 1 et 2, caractérisé en ce que l'on homopolymérise du N-vinylformamide, du N-vinyl-N-méthylformamide, de la N-vinylpyrrolidone, de l'acrylate d'hydroxyéthyle, du méthacrylate d'hydroxyéthyle, du méthacrylate de diméthylaminoéthyle, de l'acrylate de diméthylaminoéthyle, et de l'acrylate de diéthylaminoéthyle.
4. Procédé suivant les revendications 1 et 2, caractérisé en ce que l'on copolymérise du N-vinylformamide et de la N-vinylpyrrolidone, ou du N-vinylformamide et jusqu'à 90% en poids d'acétate de vinyle.
EP86114235A 1985-10-22 1986-10-15 Procédé de préparation de polymères en forme de poudre Expired EP0220603B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86114235T ATE46351T1 (de) 1985-10-22 1986-10-15 Verfahren zur herstellung von pulverfoermigen polymerisaten.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19853537455 DE3537455A1 (de) 1985-10-22 1985-10-22 Verfahren zur herstellung von pulverfoermigen homopolymerisaten
DE3537455 1985-10-22
DE3537457 1985-10-22
DE19853537457 DE3537457A1 (de) 1985-10-22 1985-10-22 Verfahren zur herstellung von pulverfoermigen copolymerisaten

Publications (2)

Publication Number Publication Date
EP0220603A1 EP0220603A1 (fr) 1987-05-06
EP0220603B1 true EP0220603B1 (fr) 1989-09-13

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Application Number Title Priority Date Filing Date
EP86114235A Expired EP0220603B1 (fr) 1985-10-22 1986-10-15 Procédé de préparation de polymères en forme de poudre

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EP (1) EP0220603B1 (fr)
CA (1) CA1262995A (fr)
DE (1) DE3665594D1 (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3609829A1 (de) * 1986-03-22 1987-09-24 Basf Ag Verfahren zur herstellung von pulverfoermigen vernetzten copolymerisaten
BR8803785A (pt) * 1987-07-30 1989-02-21 Goodrich Co B F Copolimero de acido acrilico e processo para fazer um polimero de acido acrilico
DE3909005A1 (de) * 1989-03-18 1990-09-20 Basf Ag Verwendung von nicht hydrolysierten n-vinylformamid-einheiten enthaltenden copolymerisaten als flockungs- und entwaesserungsmittel
DE3909004A1 (de) * 1989-03-18 1990-09-27 Basf Ag Verwendung von nicht hydrolysierten n-vinylformamid-einheiten enthaltenden copolymerisaten bei der papierherstellung
US5328972A (en) * 1992-09-28 1994-07-12 Rohm And Haas Company Process for preparing low molecular weight polymers
DE19618833A1 (de) * 1996-05-10 1997-11-13 Bayer Ag Verfahren zur Herstellung von Ethylen-Vinylacetat-Copolymeren
DE19833287A1 (de) 1998-07-24 2000-01-27 Basf Ag Verfahren zur Herstellung von pulverförmigen vernetzten Polymerisaten
DE10054114A1 (de) * 2000-10-31 2002-05-16 Dupont Performance Coatings Verfahren zur Herstellung von Pulverlackzusammensetzungen
DE102005053559A1 (de) 2005-11-08 2007-05-10 Basf Ag Verfahren zur Herstellung von Vinylformamid-Einheiten enthaltenden Polymerpulvern
CN105886131B (zh) * 2016-04-18 2018-08-31 广东湛丰精细化工有限公司 一种棉质活性染料清洗剂及其制备方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3522228A (en) * 1966-05-19 1970-07-28 Sumitomo Chemical Co Novel method for polymerizing a vinyl compound in the presence of a carbon dioxide medium

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Publication number Publication date
CA1262995A (fr) 1989-11-14
DE3665594D1 (en) 1989-10-19
EP0220603A1 (fr) 1987-05-06

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